CN100549130C - TCPP fire retardant preparation method - Google Patents
TCPP fire retardant preparation method Download PDFInfo
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- CN100549130C CN100549130C CNB2006100381329A CN200610038132A CN100549130C CN 100549130 C CN100549130 C CN 100549130C CN B2006100381329 A CNB2006100381329 A CN B2006100381329A CN 200610038132 A CN200610038132 A CN 200610038132A CN 100549130 C CN100549130 C CN 100549130C
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- China
- Prior art keywords
- tcpp
- aldehyde compound
- oxammonium hydrochloride
- fire retardant
- preparation
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 title claims abstract 13
- 239000003063 flame retardant Substances 0.000 title claims description 10
- -1 aldehyde compound Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000005554 pickling Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011968 lewis acid catalyst Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 9
- 150000002923 oximes Chemical class 0.000 abstract description 6
- 230000009967 tasteless effect Effects 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- STJCGBYTFNBYJS-UHFFFAOYSA-N CC(C)(Cl)OP(O)(O)=O Chemical compound CC(C)(Cl)OP(O)(O)=O STJCGBYTFNBYJS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ANHAEBWRQNIPEV-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCl ANHAEBWRQNIPEV-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N Butanol Natural products CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method that can effectively remove aldehyde compound among the TCPP, it is characterized in that after reaction obtains TCPP crude product, pickling, alkali cleaning, add the normal oxammonium hydrochloride solution reaction of aldehyde compound, wash then, distill.Thereby easy will react produce with the TCPP intermiscibility better, not segregative aldehyde compound, be transformed into water-soluble oxime, in follow-up washing, conveniently remove, make and do not contain the aldehyde compound that can produce stink substantially among the gained TCPP, even also have micro-oxime by follow-up washing, distillation, also colourless, tasteless, nontoxic because of it, and can not influence quality product.The inventive method can make that aldehyde drops to 10-20ppm by original 100ppm among the TCPP, and this is the maximum difference place that the inventive method prepares TCPP and common process gained TCPP.
Description
Technical field
The invention relates to improvement, relate in particular to a kind of preparation method that can effectively remove aldehyde compound among the TCPP phosphoric acid ester fire retardant preparation method.
Background technology
Three (chloro isopropyl) phosphoric acid ester (TCPP) is a kind of lower molecular weight phosphorus halogenated flame retardant commonly used, in urethane, plastic prod more application is arranged.Existing TCPP preparation, be by phosphorus oxychloride under lewis acid catalyst catalysis, obtain three (chloro isopropyl) phosphoric acid ester (TCPP) crude product with propylene oxide reaction, remove catalyzer through pickling, alkali cleaning, again through being washed to neutrality, branch vibration layer, distill elaboration.In this production process, have the part propylene oxide and generated valeral or the bigger aldehyde compound of molecular weight by the phosphorus oxychloride oxidation, and this aldehyde compound and TCPP have intermiscibility preferably, though through overpickling, alkali cleaning, washing and distillation, aldehyde material is not all removed in the product, and its content generally surpasses 100ppm.Yet, aldehyde compound can produce a kind of off-odor, even about 100ppm, stink is still bigger, and when making other products, stink can not volatilize, can make product send denseer stink, and long-term existence is difficult for removing, has a strong impact on quality product, when especially goods were used for automobile or finishing material, the stink existence had a strong impact on normal use.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, the not TCPP fire retardant preparation method of aldehyde-containing type compound is provided in a kind of product substantially.
The object of the invention realizes, the main improvement is to add oxammonium hydrochloride solution in reaction obtains the last handling process of TCPP crude product, make it to generate colourless, tasteless, harmless with the aldehyde cpd reaction, and water-soluble oxime, by follow-up washing process oxime is removed again, thereby obtained substantially the not TCPP of aldehyde-containing type compound.Specifically, TCPP fire retardant preparation method of the present invention, comprise that phosphorus oxychloride is under lewis acid catalyst catalysis, obtain the TCPP crude product with propylene oxide reaction, pickling, alkali cleaning, washing, distillation, it is characterized in that adding the normal oxammonium hydrochloride solution reaction of aldehyde compound after pickling, the alkali cleaning, wash then, distill.
The said lewis acid catalyst of the present invention is meant for example anhydrous aluminum chloride commonly used, titanium tetrachloride, magnesium dichloride, ferric chloride catalyst in the TCPP reaction.
The said oxammonium hydrochloride solution of the present invention, a kind of being preferably adopted its alcoholic solution, and be relatively low because of the alcoholic solution boiling point, remove in follow-up distillation easilier, and pure medium dissolves oxammonium hydrochloride again easily, not with material reaction.The present invention through test relatively more preferably adopts the alcoholic solution of 2-5 carbon atom, and it not only has lower boiling point, can avoid boiling point low excessively again simultaneously, volatilization at normal temperatures, and help environmental protection production.
The present invention adds the oxammonium hydrochloride solution reaction, and a kind of better is suitably to heat, and for example carries out in 40-60 ℃, so more helps reaction and accelerates with complete.
TCPP fire retardant preparation method of the present invention, owing to adopt and obtain crude product in reaction, pickling, after the alkali cleaning, add oxammonium hydrochloride solution, the aldehyde cpd reaction that makes it and produce generates colourless, tasteless, harmless, and water-soluble oxime, by follow-up washing process oxime is removed again, thereby easyly will be reacted produce better with the TCPP intermiscibility, not segregative aldehyde compound is transformed into water-soluble oxime, conveniently remove by follow-up washing, make not contain the aldehyde compound that produces stink substantially among the gained TCPP, even and by follow-up washing, distillation is if also exist micro-oxime, also colourless because of it, tasteless, nontoxic, and can not influence the subsequent product quality.The inventive method can make that aldehyde drops to 10-20ppm by original 100ppm among the TCPP, this is the maximum difference place that the inventive method prepares TCPP and common process gained TCPP, and the inventive method can be used for the deodorizing with similar three (chloroethyl) phosphoric acid ester of TCPP (TCEP) equally.
Below in conjunction with several embodiments, further specify preparation method of the present invention.
Embodiment
Preparation TCPP crude product: phosphorus oxychloride is added aluminum trichloride catalyst by common technology, drip propylene oxide at 60-80 ℃, keep 60-70 ℃ of temperature of reaction, after dripping oxyethane, continue 80 ℃ of reactions of insulation 1.5 hours, add diluted acid and reactant reaction, stirred 1 hour, with static 2 hours of reactant, tell sour water, crude product TCPP.
Comparative example: get the crude product TCPP200g that makes, in 500 liters three-necked bottle, add catalyzer in the dilute hydrochloric acid flush away reactant, after telling the sour water layer, add in the diluted alkaline and excessive acid, divide the lixiviating water layer, add deionized water again, material is washed till neutrality, after dividing water layer, vacuum distilling dewater the TCPP finished product, detect among the TCPP aldehyde compound content and see attached list.
Embodiment: get same crude product TCPP200g, drop in 500 liters the three-necked bottle, add catalyzer in the dilute hydrochloric acid flush away reactant, tell the sour water layer after, add in the diluted alkaline and excessive acid, divide the lixiviating water layer, in the gained organic phase, add the normal oxammonium hydrochloride solution of aldehyde compound, be warming up to 50 ℃ and stirred 30 minutes, add deionized water wash again, branch vibration layer, vacuum distilling dewater the TCPP finished product, detect among the TCPP aldehyde compound content and see attached list.
Equally, TCEP also can remove smelly aldehyde compound with same procedure.
Each comparative example and embodiment aldehyde compound detected result
| Aldehyde compound | Aldehyde compound | |||
| Comparative example 1 | 118.7ppm | Embodiment 1 | Add the 3 ‰ oxammonium hydrochloride aqueous solution | 17ppm |
| Comparative example 2 | 141.9ppm | Embodiment 2 | Add 3 ‰ oxammonium hydrochloride ethanolic solns | 6.399ppm |
| Comparative example 3 | 98.3ppm | Embodiment 3 | Add 2 ‰ oxammonium hydrochloride butanol solutions | 9.5ppm |
| Comparative example 4 | 109.3ppm | Embodiment 4 | Add 1 ‰ oxammonium hydrochloride ethanolic solns | 21.9ppm |
| Comparative example 5 | 186.7ppm | Embodiment 5 | Add 2 ‰ oxammonium hydrochloride propanol solution | 11.9ppm |
Claims (4)
1, TCPP fire retardant preparation method, comprise that phosphorus oxychloride is under lewis acid catalyst catalysis, obtain the TCPP crude product with propylene oxide reaction, pickling, alkali cleaning, washing, distillation, it is characterized in that adding the normal oxammonium hydrochloride solution reaction of aldehyde compound after pickling, the alkali cleaning, wash then, distill.
2,, it is characterized in that said oxammonium hydrochloride solution is the alcoholic solution of oxammonium hydrochloride according to the described TCPP fire retardant of claim 1 preparation method.
3, according to the described TCPP fire retardant of claim 2 preparation method, the alcoholic solution that it is characterized in that said oxammonium hydrochloride is the alcoholic solution of 2-5 carbon atom.
4, according to claim 1,2 or 3 described TCPP fire retardant preparation methods, it is characterized in that adding the oxammonium hydrochloride solution reaction and in 40-60 ℃, carry out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100381329A CN100549130C (en) | 2006-01-26 | 2006-01-26 | TCPP fire retardant preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100381329A CN100549130C (en) | 2006-01-26 | 2006-01-26 | TCPP fire retardant preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101007952A CN101007952A (en) | 2007-08-01 |
| CN100549130C true CN100549130C (en) | 2009-10-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100381329A Active CN100549130C (en) | 2006-01-26 | 2006-01-26 | TCPP fire retardant preparation method |
Country Status (1)
| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503974A (en) * | 2011-11-11 | 2012-06-20 | 江苏雅克科技股份有限公司 | Purification method of TCPP (trichloropropylphosphate) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215295B (en) * | 2007-12-27 | 2011-04-27 | 南京师范大学 | Preparation method of halogen-containing diphosphate or halogen-containing diphosphite |
| CN101775031B (en) * | 2009-12-22 | 2012-08-29 | 江苏雅克科技股份有限公司 | Method for preparing TCPP (Tris(Chloroisopropyl)Phosphate) flame retardant |
| CN102002068B (en) * | 2010-11-29 | 2012-02-22 | 浙江万盛股份有限公司 | After-treatment method of crude tris-(2-isopropyl chloride) phosphate |
| CN102807581B (en) * | 2012-08-24 | 2015-11-18 | 南京师范大学 | The preparation method of Lewis acid ion liquid catalyst synthesis phosphotriester |
| CN108794522B (en) * | 2018-05-07 | 2023-02-24 | 浙江万盛股份有限公司 | Full continuous flow production process of tris (1-chloro-2-propyl) phosphate |
| CN108864178B (en) * | 2018-07-19 | 2020-10-09 | 山东默锐科技有限公司 | A kind of microreaction method and device for synthesizing tris(2-chloropropyl) phosphate |
Citations (2)
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|---|---|---|---|---|
| US6673955B2 (en) * | 2001-11-27 | 2004-01-06 | Bayer Aktiengesellschaft | Preparation of triethyl phosphate |
| CN1544439A (en) * | 2003-11-14 | 2004-11-10 | 无锡市红星化工厂 | High purity tributyl phosphate production method |
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2006
- 2006-01-26 CN CNB2006100381329A patent/CN100549130C/en active Active
Patent Citations (2)
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|---|---|---|---|---|
| US6673955B2 (en) * | 2001-11-27 | 2004-01-06 | Bayer Aktiengesellschaft | Preparation of triethyl phosphate |
| CN1544439A (en) * | 2003-11-14 | 2004-11-10 | 无锡市红星化工厂 | High purity tributyl phosphate production method |
Non-Patent Citations (4)
| Title |
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| TCEP[三-(β-氯乙基)磷酸酯]阻燃剂的研制. 杨锦飞等.精细化工，第13卷第2期. 1996 |
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| 阻燃剂磷酸三(1-氯-2-丙基)酯合成工艺选择. 杨锦飞，杨瑶.南京师范大学学报(工程技术版)，第2卷第4期. 2002 |
| 阻燃剂磷酸三(1-氯-2-丙基)酯合成工艺选择. 杨锦飞，杨瑶.南京师范大学学报(工程技术版)，第2卷第4期. 2002 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503974A (en) * | 2011-11-11 | 2012-06-20 | 江苏雅克科技股份有限公司 | Purification method of TCPP (trichloropropylphosphate) |
| CN102503974B (en) * | 2011-11-11 | 2014-05-14 | 江苏雅克科技股份有限公司 | Purification method of TCPP (trichloropropylphosphate) |
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| CN101007952A (en) | 2007-08-01 |
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